Chloromethyl sulphide



. substituted malonic esters, V

Patented July 25, 1944 UNITED STATES PATENT l OFFICE" CHLOBOMETHYLSULPHIDE Lewis A. Walter, East Orange, N. 1., assignor to The MaltbieChemical Company, Newark, N. 1., a corporation of New Jersey No Drawing.Application Febml'y 2s,-194z, Serial No. 432,880

4.0laims.

The present invention relates to new and useful compositions of mattercomprising a series of organic compounds which I have designatedchloromethyl sulphides, according to what I believe to be the acceptedmethod oi nomenclature: but which might also be described correctly asthiomethylene chlorides. These compounds have the formula RSCHaCl isbonded to the sulphur (oi the thiomethylene group) is attached to morethan one other carbon atom (of the hydrocarbon group), such as v is thecase in secondary or tertiary hydrocarbon groups.

These novel compounds have been iound to be useful intermediates. andmay be applied with advantage in organic syntheses tor the purpose ofintroducing the RSCHz-group into organic molecules, as, for example, inthe preparation or Cholormethyl sulphides having the above generalformula have been prepared by reacting the appropriate mercaptan withtrioxylmethylene and dry hydrogen chloride gas under conditions :ehichare fully illustrated in the examples given The iollowing specificexamples are illustrative oi the novel compounds and their preparationaccording to my invention. In the examples given, the compounds arecolorless, foul-smelling liquids.

Exmu: .1

n-Batulchloromethul sulphide cmcmcmcmscmci One mole of n-buwl mercaptanand 0.387 mole oi paraiormaldehyde (trioxymethylene) are hydrogenchloride gas passed into the mixture. As soon as the parai'ormaldehydeis dissolved, the cooling bath is removed and the dry hydrogen chloridegas passed through the mixture for several hours at room temperature.The aqueous layer'oi the reacted mixture is separated therefrom and theremaining oil dried'by contact with anhydrous calcium chloride. The oilis separated irom the drying agent by filtration and iractlonallydistilled to yield n-butylchloromethyl sulphide, boiling atapproximately 64-66" C. (uncorrected) at a-pressure of about 16 mm. 0!

mercury. Exam? 2 Cuclohexylchloromethyl sulphide CHI-CH: ch, cn s 011.01

CHgC 1 One mole of cyclohexyl mercaptan and 0.367 mole ofparaiormaldehyde (trioxymethylene) are stirred and chilled in anice-salt bath and dry hydrogen chloride gas is passed into the mixture.

As soon as the paraformaldehyde is dissolved, the cooling bath isremoved and the dry hydrogen chloride gas passed through the mixture forseveral hours at room temperature. The aqueous layer of the reactedmixture is separated therefrom, and the remaining oil dried by contactwith anhydrous calcium chloride. The oil is separated from the dryingagent by filtration and fractionally distilled to yieldcyclohexylchloromethyl sulphide, boiling at approximately 101-103 C.(uncorrected) at a pressure of about 13.5 mm. of

mercury.

Exmu: 3

Tertiary butylchloromethill sulphide (cnmcscmci (a) One mole of tertiarybutyl mercaptan and 0.38! mole of paraiormaldehyde (trioxymethylene) arestirred and chilled in an ice-salt bath and dry hydrogen chloride gas ispassed into the mixture.

As soon as the paraiormaldehyde is dissolved,

the cooling bath is removed and the dry hydro- Ben chloride gas ispassed through the mixture for several hours at room temperature. The

aqueous layer oi the reacted mixture is separated stirred and chilled inan ice-salt bath and dry 50 therefrom and the remaining oil dried bycontact of mercury.

The substituent group R, as it has been described and defined above, maybe widely varied within those limits; and among the derivativesspecifically included in the invention are the 101- lowing which aregiven as illustrative examples:

RSCHzCl wherein R represents a saturated hydrocarbon n-Butyiomcmcmcmsornoi 64-66 m on, a

Isobutyl oncmscmol i'eo-iei seoondary-butylnu; CH|CH;CHBCH,CL 584 11Tertiary-butyl CH CBCH1CI -L 57-58 12 CHO l-methylbutyl CH|CH;CH1CHSCHCL 73-76 13 Ha I n-Amyl CHrCHgCHzCHgCHgSCHgCl 170-176 IsoamylCHgCHCHgCHzSCHgCL'. I 91-03 30 n-Hexyl CHICHICHICHICHICHlSCHIC] 105-10622 OKs-CH: h Cyclohexyi 0Q, CHscmci 101-103 13.5

CH,-C

2-ethylbutyi CH|CH|CHCHgSOH|CL 87-88 9 1 l-methylheptyi. i. 7H|(CH1)sCHS CHaOl 50-53 1.5

1 Atmospheric. I

In the foregoing examples, the boiling points are approximate, and atabout the pressures given; but are the boiling points which I actuallyobserved, according to a procedure believed to be reliable.

The examples given above, and illustrative processes for theirproduction, include the best embodiments of my present invention nowknown to me; but it is to be understood that the invengroup containingmore than three but not more than eight carbon atoms, and has asecondary carbon atom attached directly to the sulphur oi thethiomethylene group.

2. l-methylbutyl chloromethyl sulphide.

3. Secondary-butyl chloromethyl sulphide.

4. Cyclohexyl chloromethyl sulphide.

mwrs A. wAL'raa.

